Herbicidal phenoxypropionic acid N-alkyl-N-2-fluorophenyl amide compounds

ABSTRACT

The present invention relates to novel herbicidal phenoxypropionic acid N-alkyl-N-2-fluorophenyl amide compounds represented in the following formula (1), a method for preparing thereof, their use to control barnyard grass produced from rice and composition as suitable herbicides.                    
     wherein, 
     R is methyl or ethyl group; 
     X is hydrogen, halogen, cyano, C 1 ˜C 6  alkyl, C 1 ˜C 6  alkoxy, C 1 ˜C 3  haloalkyl substituted with 1 to 3 of halogen atom(s), C 1 ˜C 3  haloalkoxy substituted with 1 to 3 of halogen atom(s), C 2 ˜C 4  alkoxyalkoxy, phenox,benzyloxy, C 2 ˜C 6  alkenyl, C 2 ˜C 6  alkinyl, C 2 ˜C 6  alkenyloxy, C 2 ˜C 6  alkinyloxy, or phenyl group; 
     Y is hydrogen or fluoro; 
     n is an integer of 1 or 2 and when n is 2, X can be in a combination of other substituents.

This application is a division of application Ser. No. 09/744,450, filedFeb. 20, 2001, now U.S. Pat. No. 6,486,098which is a 371 ofPCT/KR99/00401 filed Jul. 24, 1999 the entire contents of which areincorporated herein.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to novel herbicidal phenoxypropionic acidN-alkyl-N-2-fluorophenyl amide compounds represented in the followingformula (1), a method for preparing thereof, their use to controlbarnyard grass produced from rice and composition as suitable herbicides

wherein,

R is methyl or ethyl group;

X is hydrogen, halogen, cyano, C₁˜C₆ alkyl, C₁˜C₆ alkoxy, C₁˜C₃haloalkyl substituted with 1 to 3 of halogen atom(s), C₁˜C₃ haloalkoxysubstituted with 1 to 3 of halogen atom(s), C₂˜C₄ alkoxyalkoxy, phenoxy,benzyloxy, C₂˜C₆ alkenyl, C₂˜C₆ alkinyl, C₂˜C₆ alkenyloxy, C₂˜C₆alkinyloxy, or phenyl group;

Y is hydrogen or fluoro;

n is an integer of 1 or 2 and when n is 2, X can be in a combination ofother substituents.

2. Description of the Prior Art

U.S. Pat. No. 4, 130,413 discloses the compound containing the followingformula (2).

wherein, (R₁)_(m) is hydrogen, halogen, CF₃, NO₂, CN or alkyl group; Ais O, S or NH; R₂ is hydrogen or alkyl group; Z is

(where R₃ and R₄, that are the same or different, are hydrogen, C₁˜C₆alkyl, C₁˜C₆ hydroxyalkyl, C₃˜C₆ cycloalkyl, C₁˜C₄ alkoxy, or phenylsubstituted where 1 to 3 sbstituents are selected from C₁˜C₄ alkylgroup, C₁˜C₆ alkoxy group, halogen and CF₃.

U.S. Pat. No. 4,531,969 discloses the compounds containing the followingformula (3).

wherein, R₅ is

(where R₆ is hydrogen or halogen atom, R₇ is hydrogen or alkyl group); Zis the same as defined above.

U.S. Pat. No. 5,254,527 discloses the compounds containing the followingformula (4).

wherein, R₅ and Z are the same as defined above.

None of the patents teaches the synthesis of the compound represented inthe above formula (1) and have tested the same for herbicidal activity.

JP Patent publication 2-11580 discloses the compound represented in thefollowing formula (5).

wherein, L is lower alkyl, halogen, methoxy, methoxyphenoxy, methylthioor methylvinyl group; n is an integer of 0 to 2.

JP Patent publication sho 53-40767 and sho 54-112828 also disclose thatphenoxypropionic acid amide derivatives have herbicidal activity.

However, none of reports including the patents mentioned above hastaught a method for preparing the compounds in the above formula (1) andtested the same against herbicidal activity. And also it has not beenreported that the compounds have superior herbicidal activity andselectivity toward rice and control barnyard grass produced from rice.

SUMMARY OF THE INVENTION

Even though many of herbicides for rice have been recently developed andused, barnyard grass among weeds is the biggest problem in rice paddy.

Development of herbicides to control barnyard grass is an urgent to onewho is in the field of agriculture. After transplanting young rice,herbicides, developed until now, cannot effectively control theproduction of barnyard grass so that it causes a huge damage to harvest.It has been reported that when barnyard grass is produced for one weekin 1 m², amount of harvest decreases by 2%, for 5 weeks by about 10%,for 10 weeks by 19% and for 20 weeks by 35%

Many herbicides have been used for the purpose of controlling barnyardgrass that damages in amount of harvest of rice. However, the herbicidewith a broader herbicidal activity, environmentally-friendly propertyand cost-effectiveness is still in demand.

The inventors have intensively studied to prepare herbicides toeffectively control barnyard grass. As a result, they completed thisinvention to find a novel phenoxypropionic acid N-alkyl-N-2-fluorophenylamide and its derivatives that are stable to rice and selectivelycontrol barnyard grass. This superior effectiveness is distinguishedfrom the conventional inventions.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is characterized by novel phenoxypropionic acidN-alkyl-N-2-fluorophenyl amide represented in the following formula (1)with an excellent herbicidal activity as well as selectively stabletoward rice.

wherein, R, X, Y and n are the same as previously defined.

The compounds of the formula (1) according to tile present invention maybe specified as the following Table 1.

TABLE 1 (I) 

R Y X CH₃ H H CH₂CH₃ H H CH₃ H 4-CN CH₃ H 4-F CH₃ H 3-F CH₃ H 5-F CH₃ H4-Cl CH₃ H 4,5-F₂ CH₃ H 4-Br CH₃ H 4-phenyl CH₃ H 4-CH₃ CH₃ H 3-Br CH₃ H4-CH₂CH₃ CH₃ H 4-propyl CH₃ H 4-isopropyl CH₃ H 4-cyclopropyl CH₃ H4-butyl CH₃ H 4-isobutyl CH₃ H 3-CN CH₃ H 4-OCH₃ CH₃ H 4-O-phenyl CH₃ H4-OEt CH₃ H 4-O-isopropyl CH₃ H 4-O-allyl CH₃ H 4-O-propyl CH₃ F H CH₃ F3-F CH₃ F 4-F CH₂CH₃ F 4-F CH₃ F 4-Cl CH₃ F 4-Br CH₃ F 4-CH₃ CH₃ F4-CH₂CH₃ CH₃ F 4-propyl CH₃ F 4-isopropyl CH₃ F 4-cyclopropyl CH₃ F4-butyl CH₃ F 4-isobutyl CH₃ F 4-OCH₃ CH₃ F 4-OEt CH₃ F 4-O-isopropylCH₃ F 4-O-propyl CH₃ H 3,5-F₂ CH₃ H 5-F CH₃ H 5-Cl CH₃ H 5-Br CH₃ H 5-CNCH₃ H 5-CH₃ CH₃ H 5-CH₂CH₃ CH₃ H 5-phenyl CH₃ H 5-propyl CH₃ H5-isopropyl CH₃ H 5-cyclopropyl CH₃ H 5-butyl CH₃ H 5-isobutyl CH₃ H5-OCH₃ CH₃ H 5-OEt CH₃ H 5-O-isopropyl CH₃ H 5-O-propyl CH₃ H 5-O-phenylCH₃ H 5-O-allyl CH₃ F 5-H CH₃ F 5-F CH₃ F 5-Cl CH₃ F 5-Br CH₃ F 5-CH₃CH₃ F 5-CH₂CH₃ CH₃ F 5-propyl CH₃ F 5-isopropyl CH₃ F 5-cyclopropyl CH₃F 5-n-butyl CH₃ F 5-isobutyl CH₃ F 5-OCH₃ CH₃ F 5-OEt CH₃ F5-O-isopropyl CH₃ F 5-O-propyl

The compounds of formula (1) according to this invention can besynthesized by a conventional method represented in the following scheme1, reacting a compound of the formula (6) with a compound of the formula(7)

wherein, X′ is OH, Cl, Br or phenoxy, group; R, X, Y and n are the sameas previously defined.

In the method according to scheme 1, it is prefer to use a binder suchas triphenylphosphine and an organic base such as triethylamine orpyridine by keeping, temperature at 0˜100° C. in an inert solvent suchas ethers like tetrahydrofuran, ethyethyl acetate, acetonitrile,toluene, xylene, hexane, methylene chloride, carbon tetrachloride,dichloroethane or the like, and to purify the crude product by columnchromatography.

Another method for preparing the compounds (1) represented in thefollowing scheme 2 is an alkylation of a compound of the formula (8) tocompounds of the formula (9).

wherein, X″, which is a leaving group, is Cl, Br, I, benzenesulfonyloxy,toluenesulfonyloxy methanesulfonyloxy or lower alkyl sulfate group R,X,Yand n are the same as previously defined.

In scheme 2, it is prefer to use a strong base which is enough to pullout a hydrogen from amide, NH. The strong base used in this invention isNaOH, KOH, LiOH, NaH, n-BuLi or LDA. It is prefer to carry this reactionat the temperature of −78˜50° C. in an inert solvent such as ethers likeethylether, dioxane or tetrahydrofuran or hydrocarbons like hexane.

Another method for preparing the compounds (1) represented in thefollowing scheme 3 is a reaction of a compound of the formula (10) witha compound of the formula (11) in the presence of a base.

wherein, Y′ is halogen, alkylsulfonyloxy, haloalkylsulfonyloxy,benzenesulfonyloxy or toluenesulfonyloxy group; R, X, Y, and n are thesame as previously defined.

In Scheme 3, it is prefer to use inorganic bases such as alkali metalhydroxides like sodium hydroxide or potassium hydroxide, alkali metalcarbonates like sodium carbonate or potassium carbonate, alkali metalhydrogencarbonates like sodium hydrogencarbonate or potassiumhydrogencarbonate or organic bases like triethylamine,N,N-dimethylaniline, pyridine or 1,8-diazabicyclo[5,4,0]undec-7-ene.

A phase transition catalyst such as tetra-n-butylammonium bromide or18-crown-6-[1,4,7,10,13,16-hexaoctacyclooctadecane]can be added tocomplete a reaction rapidly, if necessary. And also one or more than twosolvents can combined and used, if deemed necessary. It is prefer to usean inert organic solvent; for example, ketones such as acetone; aromatichydrocarbons such as toluene, xylene or chlorobenzene; aliphatichydrocarbons such as petroleum ether or ligroin; ethers such asdiethylether, tetrahydrofuran or dioxane; nitriles such as acetonitrileor propionitrile; or amides such as N,N-dimethylfomamide,N,N-dimethylacetamide, N-methylpyrrolidone. A reaction is carried at thetemperature of from 0° C. to reflux, preferably 5˜50° C. for 1 to24hour(s) to afford a high yield.

Another method for preparing the compound (1) represented in thefollowing scheme 4 is a reaction of a compound of the formula (12) witha compound of the formula (13) in the presence of a base.

wherein, X, Y, Y′, R and n are the same as previously defined.

In Scheme 4, it is prefer to use inorganic bases; for example; alkalimetal hydroxides such as sodium hydroxide or potassium hydroxide, alkalimetal carbonates such as sodium carbonate or potassium carbonate, alkalimetal hydrogencarbonates such as sodium hydrogencarbonate or potassiumhydrogencarbonate or organic bases such as triethylamine,N,N-dimethylaniline, pyridine, picoline, quinoline, or1,8-diazabicyclo[5,4,0] undec-7-ene.

A phase transition catalyst such as tetra-n-butylammonium bromide or18-crown-6[1,4,7,10,13,16-hexaoctacyclooctadecane] can be used, ifnecessary And also one or more than two solvents can be combined andused if deemed necessary. It is prefer to use an inert organic solvent;for example; ketones such as acetone or butanone; aromatic hydrocarbonssuch as benzene, toluene, xylene or chlorobenzene; aliphatichydrocarbons such as petroleum ether, or ligroin; ethers such asdiethylether, tetrahydrofuran or dioxane; nitriles such as acetonitrileor propionitrile; or amides such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methylprrolidone. A reaction is carried at thetemperature of from 0° C. to reflux, preferably 20˜100° C. for 1 to 24hour(s) to afford a high yield.

The present invention is explained in more detail by the followingexamples but is not limited by these examples.

EXAMPLE 1 N-(2-Fluorophenyl)-N-methyl-2-bromo-propionamide

2-Bromopropionic acid (3.4 g, 0.022 mol) and N-methyl-2-fluoroaniline(3g. 0.024 mol) were dissolved in 50 ml of chloroform and cooled to 0° C.A solution of dicyclohexylcarbodiimide(5 g, 0.024 mol) in 10 ml ofchloroform was slowly injected through a syringe. A temperature of thereaction mixture was raised to room temperature and it was stirred for 1hour. Solid remained during the reaction was filtered out and washedtwice with 20 ml of chloroform. The filtrate was concentrated underreduced pressure and the crude product was purified by columnchromatography (eluent; ethyl acetate/n-hexane=⅓) to afford 5 g of thetarget product.

¹H-NMR(CDCl₃): δ 1.7 (3H, d), 3.24 (3H, s), 4.16 (0.7H, q), 4.34 (0.3H,q), 7.13˜7.48 (4H, m).

EXAMPLE 2 N-(2-Fluorophenyl)-N-methyl-2-(4-hydroxyphenoxy)propionamide

N-(2-fluorophenyl)-N-methyl-2-bromo-propionamide(18.2 g, 0.07 mol),hydroquinone(7 g, 0.064 mol), potassium carbonate(10.54 g, 0.076 mol)and tetra-n-butylammonium bromide(1 g) were dissolved in 350 ml ofacetonitrile and heated at reflux for 6 hours. The reaction mixture wascooled to room temperature and solid remained during the reaction wasfiltered out. The filtrate was concentrated under reduced pressure andthe crude product was purified by column chromatography(eluent: ethylacetate/n-hexane=½) to afford 16 g of the target product.

¹H-NMR(CDCl₃): δ 1.42 (3H, t), 3.25 (3H, s), 4.56 (1H, q), 6.5˜7.4 (8H,m).

EXAMPLE 3 2-[4-(6-Chloro-2-benzoxazoyloxy)-phenoxy] propionicAcid-N-(2-fluorophenyl)-N-methylamide

N-(2-fluorophenyl)-N-methyl-2-(4-hydroxyphenoxy)propionamide (11.5 g,0.04 mol), 2,6-dichlorobenzoxazole (6.85 g, 0.036 mol), potassiumcarbonate (6 g, 0.043 mol) and tetra-n-butylammonium bromide (1 g) weredissolved in 300 ml of acetonitrile and heated at reflux for 7 hours.The reaction mixture was cooled to room temperature and solid remainedduring the reaction was filtered out. The filtrate was concentratedunder reduced pressure and the crude product was purified by columnchromatography (eluent: ethyl acetate/n-hexane=⅓) to afford 12.5 g ofthe target product.

¹H-NMR(CDCl₃): δ 1.42 (3H, t), 3.3 (3H, s), 4.62 (1H, m), 6.8˜7.4 (11H,m).

EXAMPLE 4 2-[4-(6-Chloro-2-benzoxazoyloxy)-phenoxy]propionicAcid-N-(2-fluorophenyl)amide

2-[4-(6-chloro-2-benzoxazoyloxy)-phenoxy]propionic acid (346.7 mg, 1mmol) was dissolved in 10 ml of tetrahydrofuran 2-fluoroaniline(111.12mg, 1 mmol), triphenylphosphine(393.4 mg, 1.5 mmol), triethylamine(0.15ml, 1 mmol) and carbon tetrachloride(1 ml) were added sequentially andheated at reflux for 8 hours. The reaction mixture was cooled to roomtemperature and acidified with 5% hydrochloric acid, followed byaddition of water. The acidified reaction mixture was extracted threetimes with ethyl acetate. The combined organic solvent layer was driedover magnesium sulfate, filtered and concentrated under reducedpressure. The crude product was purified by columnchromatography(eluent: ethyl acetate/n-hexane=¼) to afford 200 mg of thetarget product.

m.p: 132˜136° C.

¹H-NMR(CDCl₃): δ 1.7 (3H, d), 4.81 (1H, q), 7.05˜7.45 (10H, m), 8.35(1H, m), 8.5 (1H, br).

EXAMPLE 5 2-[4-(6-Chloro-2-benzoxazoyloxy)-phenoxy]propionicAcid-N-(2-fluorophenyl)-N-methyl Amide

2-[4-(6-chloro-2-benzoxazoyloxy)-phenoxy]propionicacid-N-(2-fluorophenyl)amide (100 mg, 0.24 mmol) was dissolved in 10 mlof anhydrous tetrahydrofuran and 60% NaH(10 mg, 0.24 mmol) and CH₃I(34mg, 0.24 mmol) were added sequentially at 0° C. The reaction mixture wasstirred at room temperature for 5 hours. Ice water was poured to thereaction mixture and it was extracted three times with ethyl acetate;The combined organic solvent layer was dried over magnesium sulfate,filtered and concentrated under reduced pressure. The crude product waspurified by column chromatography(eluent: ethyl acetate/n-hexane=¼) toafford 75 mg of the target product.

¹H-NMR(CDCl₃): δ 1.42 (3H, t), 3.3 (3H, s), 4.62 (1H, m), 6.8˜7.4 (11H,m).

EXAMPLE 6 2-[4 (6-Chloro-2-benzoxazoyloxy)-phenoxy]propionicAcid-N-(2-fluorophenyl)-N-methyl Amide

2-[4-(6-chloro-2-benzoxazoyloxy)-phenoxy]propionic acid(346.7 mg, 1mmol) was dissolved in 10 ml of tetrahydrofuran andN-methyl-2-fluoroaniline(125 mg, 1 mmol), triphenylphosphine(393.4 mg,1.5 mmol), triethylamine(0.15 ml, 1 mmol) and carbon tetrachloride(1 ml)were added sequentially and the reaction was heated at reflux for 12hours. The reaction mixture was cooled to room temperature and acidifiedwith 5% hydrochloric acid, followed by addition of water. The acidifiedreaction mixture was extracted three times with ethyl acetate. Thecombined organic solvent layer was dried over magnesium sulfate,filtered and concentrated under reduced pressure. The crude product waspurified by column chromatography(eluent: ethyl acetate/n-hexane=½) toafford 100 mg of the target product.

EXAMPLE 7 2-[4-(6-Chloro-2-benzoxazoyloxy-phenoxy] propionicAcid-N-ethyl-N-(2-fluorophenyl)amide

2-[4(6-choro-2-benzoxazoyloxy)-phenoxy]-N-(2-fluorophenyl)propionamide(100mg, 0.24 mmol) was dissolved in 10 ml of anhydrous tetrahydrofuran and60% NaH(10 mg, 0.24 mmol) and bromoethane(27 mg, 0.24 mmol) were addedsequentiall at 0° C. and then the reaction mixture was stirred at roomtemperature for 8 hours. Ice water was poured to the reaction mixtureand it was extracted three times with ethyl acetate. The combinedorganic solvent layer was dried over magnesium sulfate, filtered andconcentrated under reduced pressure. The crude product was purified bycolumn chromatography(eluent: ethyl acetate/n-hexane=½) to afford 60 mgof the target product.

¹H-NMR(CDCl₃): δ 1.1 (3H, t), 1.42 (3H, d), 3.8 (2H, q), 4.62 (1H, q),6.7˜7.4 (11H, m).

EXAMPLE 8 2-[4 (6-Chloro-2-benzoxazoyloxy)-phenoxy]propionicAcid-N-methyl-N-(2,4,5-trifluorophenyl)amide

2-[4-(6chloro-2-benzoxazoyloxy)-phenoxy]propionic acid(0.693 g, 2 mmol)was dissolved in 15 ml of tetrahydrofuran andN-methyl-2,4,5-trifluoroaniline(0.322 g, 2 mmol),triphenylphosphine(0.78g, 2 mmol), triethylamine(0.4 ml) and carbontetrachloride(2 ml) were added sequentially and then the reactionmixture was heated at reflux for 18 hours. The reaction mixture wascooled to room temperature and acidified with 5% hydrochloric acid. Theacidified reaction mixture was extracted three times with etheylacetate. The combined organic solvent layer was dried over magnesiumsulfate, filtered and concentrated under reduced pressure. The crudeproduct was purified by column chromatography(eluent: ethylacetate/n-hexane=½) to afford 250 mg of the target product.

¹H-NMR(CDCl₃): δ 1.42 (3H, d), 3.2 (3H, s), 4.65 (1H, m), 6.6˜7.4 (9H,m).

EXAMPLE 9 2-[4 (6-Chloro-2-benzoxazoyloxy)-phenoxy]propionicAcid-N-methyl-N-(2,6-difluoro-phenyl)amide

2-[4-(6-chloro-2-benzoxazoyloxy)-phenoxy]propionic acid(0.693 g, 2 mmol)and N-methyl-2,6-difluoroaniline(0.284 g, 2 mmol) were dissolved in 20ml of tetrahydrofuran and triphenylphosphine(0.78 g, 2 mmol),triethylamine(0.42 ml) and carbon tetrachloride(2 ml) were addedsequentially. The reaction mixture was heated at reflux for 16 hours.The reaction mixture was cooled to room temperature and acidified with5% hydrochloric acid. The acidified reaction mixture was extracted threetimes with ethyl acetate. The combined organic solvent layer was driedover magnesium sulfate, filtered and concentrated under reducedpressure. The crude product was purified by columnchroniatography(eluent: ethyl acetate/n-hexane=½) to afford 205 mg ofthe target product.

¹H-NMR(CDCl₃): δ 1.4 (3H, d), 3.3 (3H, s), 4.62 (1H, q), 6.8˜7.4 (10H,m).

EXAMPLE 10 2-[4-(6-Chloro-2-benzoxazoyloxy)-phenoxy]propionicAcid-N-(2,4-difluorophenyl)-N-methyl Amide

2-[4-(6-chloro-2-benzoxazoyloxy)-phenoxy]propionic acid(0.693 g, 2 mmol)was dissolved in 15 ml of tetrahydrofuran andN-methyl-2,4-difluoroaniline(0.284 g, 2 mmol), triphenylphosphine(0.78g, 2 mmol), triethylamine(0.42 ml) and carbon tetrachloride(2 ml) wereadded sequentially. The reaction mixture was heated at reflux for 16hours. The reaction mixture was cooled to room temperature and acidifiedwith 5% hydrochloric acid, followed by addition of water. The acidifiedreaction mixture was extracted three times with ethyl acetate. Thecombined organic solvent latter was dried over magnesium sulfate,filtered and concentrated under reduced pressure. The crude product waspurified by column chromatography(eluent: ethyl acetate/n-hexane=½) toafford 230 mg of the target product.

¹H-NMR(CDCl₃): δ 1.4 (3H, d), 3.2 (3H, s), 4.6 (1H, q), 6.6˜7.2 (10H,m).

EXAMPLE 11 2-[4-(6-Chloro-2-benzoxazoyloxy)-phenoxy]propionicAcid-N-methyl-N-(2,3,6-trifluorophenyl)amide

2-[4-(6-chloro-2-benzoxazoyloxy)-phenox]propionic acid(0.693 g, 2 mmol)was added to 6 ml of thionyl chloride and the reaction mixture washeated at reflux for 2 hours. Excess of thionyl chloride was removedunder reduced pressure and 3 ml of anhydrous tetrahydrofuran was addedto it. A solution of N-methyl-2,3,6-trifluoroaniline(0.32 g, 2 mmol) andtriethyl amine(0.42 ml) in anhydrous tetrahydrofuran(10 ml) was addedslowly to the reaction mixture at 0° C. The mixture was stirred at 0° C.for 30 minutes and stirred at room temperature for additional 1 hour.After Souring water the reaction mixture was extracted three times withethyl acetate. The combined organic solvent layer was dried overmagnesium sulfate, filtered and concentrated under reduced pressure. Thecrude product was purified big column chromatography(eluent: ethylacetate/n-hexane=½) to afford 240 mg of the target product.

¹H-NMR(CDCl₃): δ 1.45 (3H, d), 3.25 (3H, s), 4.6 (1H, q), 6.7 7.4 (9H,m).

EXAMPLE 12˜17

The compounds represented in the following Table 2 were prepared by thesame procedure of example 11 except using of aniline compounds insteadof N-methyl-2,3,6-trifluoroaniline.

TABLE 2

Example X₁ X₂ ¹H-NMR(CDCl₃) Exam. 12 H CH₃ 1.42(3H, t), 2.3(3H, s),3.25(3H, s), 4.62(1H, m), 6.8˜7.4(10H, m) Exam. 13 Cl H 1.42(3H, t),3.3(3H, s), 4.62(1H, m), 6.7˜7.5(10H, m) Exam. 14 H F 1.42(3H, t),3.3(3H, s), 4.62(1H, m), 6.5˜7.4(10H, m) Exam. 15 CH₃ H 1.42(3H, t),2.38(3H, s), 3.25(3H, s), 4.62(1H, m), 6.8˜7.4(10H, m) Exam. 16 OCH₃ H1.42(3H, t), 3.25(3H, s), 3.8(3H, s), 4.65(1H, m), 6.65˜7.45(10H, m)Exam. 17 OCH₂CH₃ H 1.25(3H, t), 1.42(3H, t), 3.25(3H, s), 4.0(2H, q),4.62(1H, m), 6.65˜ 7.42(10H, m)

Formulation

In order to use the compounds according, to the present invention asherbicides, they should be formulated in such a suitable type such aswettable powder, emulsions, granules, dusts, suspensions and solutionsby combining a carrier, a surfactant, a dispersing agent or a supplementagent. Many of these may be applied directly or after diluted withsuitable media. Formulations can be prepared at spray volume of fromhundreds liters to thousands liters per hectare. The formulationscontain about 0.1% to 99% by weight of active ingredient(s) and 0.1% to20% surfactant(s) or 0% to 99.9% solid or liquid diluent(s) arerecommended to be added. The formulations will contain these ingredientsin the following approximate proportions shown in Table 3.

TABLE 3 Weight Percent (%) Formulations Active ingredient DiluentSurfactant Wettable powders 10˜90  0˜74 1˜10 Suspension  3˜50 40˜95 0˜15Emulsions- Solution  3˜50 40˜95 0˜15 Granules 0.1˜95   5˜99.9 1˜15

The proportion of active ingredients is depending on the intended use.Higher ratios of a surfactant to active ingredients are sometimesdesirable and are achieved by incorporation into the formulation or tankmixing.

Solid diluents with high absorption are preferred for wettable powders.Liquid diluents and solvents are preferably stable against phaseseparation at 0° C. All the formulations may contain a small amount ofadditives to prevent forming, caking, corrosion and growth ofmicroorganisms.

According to conventional methods to prepare the composition, solutionscan be made only by blending ingredients and fine solids by blending andpulverizing with hammer-mill. Suspensions can be made by wet-milling andgranules can be made by spraying the active ingredients on performedgranular carrier.

Preparation examples of typical formulations are as follows.

Formulation 1: Wettable Powders

The ingredients are thoroughly blended, re-blended after spraying liquidsurfactant on the solid ingredients and hammer-milled until all thesolids are essentially under 100 μm.

Active ingredient (Example 3 Compound) 20 wt % Dodecylphenolpolyethylene glycol ether  2 wt % Sodium ligninsulfonate  4 wt % Sodiumsilicon aluminate  6 wt % Montmorillonite 68 wt %

Formulation 2: Wettable Powders

The ingredients are blended, hammer-milled until all the solids areunder 25 μm and packaged.

Active ingredient (Example 3 Compound) 80 wt % Sodium alkylnaphthalenesulfonate  2 wt % Sodium ligninsulfonate  2 wt % syntheticamorphous silica  3 wt % Kaolinite 13 wt %

Formulation 3: Emulsions

The ingredients are mixed and homogeneously dissolved to give emulsions.

Active ingredient (Example 3 Compound) 30 wt % Cyclohexanone 20 wt %Polyoxyethylene alkylaryl ether 11 wt % Calcium alkylbenzenesulfonate  4wt % Methylnaphthalene 35 wt %

Formulation 4: Granules

The ingredients were thoroughly blended 20 Weight part of water wasadded to 100 weight part of the ingredient mixture. The ingredientmixture was granulated with a size of 14 to 32 mesh by using extrusivegranulator and dried.

Active ingredient (Example 3 Compound) 5 wt % Sodiumlaurylalcoholsulfonate 2 wt % Sodium ligninsulfonate 5 wt %Carboxymethyl cellulose 2 wt % Potassium sulfate 16 wt %  Plaster 70 wt% 

The formulations according to this invention were sprayed with dilutingto a certain concentration.

Utility

The compounds according to the present invention represent high activityas leaf treatment herbicides for rice and especially effective in ricedue to an excellent control of barnyard grass.

The active ingredients can be used from 10 g to 4 kg per hectare,preferably from 50 g to 400 g. The amount of the compounds of thepresent invention depends on the amount and size of weeds andformulations. The herbicides of the present invention can be used asalone or in combination with other herbicides, insecticides orbactericides. Especially it is essential to add one or more of agentsselected from the group consisting of bentazon, Quinclorac, propanil,simetryn, 2,4-D, fenoxaprop-ethyl, linuron, MCPA, azafenidin,carfentrazone, molinate, thiobencarb, pendimethalin, bensulfuron-methyl,pyrazosulfuron-ethyl, metsulfuron-methyl, thifensulfuron-methyl,tribenuron-methyl, trifluralin, amidosulfuron, bromoxynil, butachlor,mecoprop, metribuzin, bifenox, benfuresate, isoproturon,cyhalofop-butyl, mefenaset, fentrazamide, pyriminobac-methyl, bispyribacsodium, azimsulfruon, cyclosulfamuron and pyanchor.

The herbicidal effect of the compounds of this invention was tested andthe examples are as follows.

Experimental Example 1: Leaf Treatment Test

Seeds of rice, wheat, barley, corn, cotton, barnyard grass, commonsorgum, large crabgrass and fall panicum were seeded at a pot with asurface area of 600 cm′. When barnyard grass kept at 20˜30° C. had threeleaves, wettable powders prepared by mixing 1 weight part of the activecompound, 5 weight part of acetone and 1 weight part of emulsifier anddiluted with water was applied directly on the leaves in 2000 l perhectare. The concentration of the spray liquid was so chosen theparticular amounts of the active compound desired 14 days after thetreatment, the degree of damage to the plants was rated in % damage incomparison to the development of untreated control.

 0 % no action (like untreated control)  20 % slight effect  70 %herbicidal effect 100 % total destruction

In the test, the active compound(s) of the formula (1) according to theinvention exhibited an excellent selectivity toward the plants andherbicidal activity against weeds.

The plants employed in this test are as follows.

TABLE 4 ABRV. SCIENTIFIC NAME ENGLISH NAME ZEAMX Zea mays L. Corn GLXMAGlycine max (L.) MERR Soy bean GOSHI Gossypium Cotton TRZAW Triticumaestivum L. Wheat ORYSA Oryza sativa L. cv. Dongjin Rice SORBIAndropogon sorghum Common sorgum ECHCG Echinochloa crus-galli Beauv var.Barnyard grass caudata Kitagawa DIGSA Digitaria Sanguinalis (L.) SCOPLarge crabgrass PANDI Panicum dichotomiflorum Michx Fall panicum

Among the compounds of the formula (1), herbicidal activity of thecompounds in table 5 is represented in the following table 6 and 7.

TABLE 5 (1)

Compound No. R Y X 1 CH₃ H H 2 CH₂CH₃ H H 3 CH₃ H 4,5-F₂ 4 CH₃ F H 5 CH₃H 4-F 6 CH₃ F 3-F 7 CH₃ H 5-CH₃ 8 CH₃ H 4-Cl 9 CH₃ H 5-F 10  CH₃ H 4-CH₃11  CH₃ H 4-OCH₃ 12  CH₃ H 4-OCH₂CH₃ control 1 H H H control 2(Fenoxaprop-ethyl)

TABLE 6 Treated amount (kg/ha) Active Compound Weeds 0.4 0.1 0.025Compound No. 1 ZEAMX 100 70 0 GLXMA 20 0 0 GOSHI 0 0 0 TRZAW 0 0 0 ORYSA0 0 0 SORBI 100 100 100 ECHCG 100 100 90 DIGSA 100 100 100 PANDI 100 100100 Compound No. 2 ZEAMX 70 10 5 GLXMA 10 0 0 GOSHI 0 0 0 TRZAW 0 0 0ORYSA 0 0 0 SORBI 100 95 40 ECHCG 95 80 20 DIGSA 100 95 30 PANDI 100 1000 Compound No. 3 ZEAMX 0 0 0 GLXMA 10 0 0 GOSHI 0 0 0 TRZAW 0 0 0 ORYSA10 0 0 SORBI 100 100 40 ECHCG 95 60 0 DIGSA 100 90 30 PANDI 0 0 0Compound No. 4 ZEAMX 100 40 10 GLXMA 20 0 0 GOSHI 0 0 0 TRZAW 0 0 0ORYSA 30 20 0 SORBI 100 100 95 ECHCG 100 95 80 DIGSA 100 100 90 PANDI100 100 40 Compound No. 5 ZEAMX 100 30 0 GLXMA 0 0 0 GOSHI 0 0 0 TRZAW 00 0 ORYSA 0 0 0 SORBI 100 100 100 ECHCG 100 100 0 DIGSA 100 100 100PANDI 100 80 40 Compound No. 6 ZEAMX 100 100 30 GLXMA 0 0 0 GOSHI 0 0 0TRZAW 0 0 0 ORYSA 20 0 0 SORBI 100 100 100 ECHCG 100 100 95 DIGSA 100100 40 PANDI 100 100 40 Compound No. 7 ZEAMX 0 0 0 GLXMA 10 0 0 GOSHI 00 0 TRZAW 0 0 0 ORYSA 0 0 0 SORBI 100 95 10 ECHCG 40 40 20 DIGSA 100 100100 PANDI 100 100 100 Compound No. 8 ZEAMX 0 0 0 GLXMA 0 0 0 GOSHI 0 0 0TRZAW 0 0 0 ORYSA 0 0 0 SORBI 100 70 0 ECHCG 70 0 0 DIGSA 100 95 30PANDI 100 0 0 Compound No. 9 ZEAMX 100 0 0 GLXMA 0 0 0 GOSHI 0 0 0 TRZAW0 0 0 ORYSA 20 0 0 SORBI 100 100 90 ECHCG 80 80 70 DIGSA 100 100 100PANDI 100 100 90 Compound No. 10 ZEAMX 0 0 0 GLXMA 0 0 0 GOSHI 0 0 0TRZAW 0 0 0 ORYSA 0 0 0 SORBI 100 60 30 ECHCG 80 0 0 DIGSA 100 95 70PANDI 70 0 0 Compound No. 11 ZEAMX 0 0 0 GLXMA 0 0 0 GOSHI 0 0 0 TRZAW 00 0 ORYSA 0 0 0 SORBI 70 20 0 ECHCG 40 0 0 DIGSA 95 95 95 PANDI 40 20 —Compound No. 12 ZEAMX 0 0 0 GLXMA 0 0 0 GOSHI 0 0 0 TRZAW 0 0 0 ORYSA 000 0 SORBI 30 0 0 ECHCG 30 0 0 DIGSA 100 100 80 PANDI 0 0 0 control 1ZEAMX 100 100 100 GLXMA 40 30 0 GOSHI 0 0 0 TRZAW 30 20 0 ORYSA 70 50 35SORBI 100 100 100 ECHCG 100 100 100 DIGSA 100 100 100 PANDI 100 100 100control 2 ZEAMX 100 100 80 GLXMA 30 0 0 GOSHI 0 0 0 TRZAW 70 60 0 ORYSA90 70 40 SORBI 100 100 100 ECHCG 100 100 100 DIGSA 100 100 100 PANDI 100100 95

TABLE 7 Treated amount (kg/ha) Active Compound 4 Leaves 1.0 0.25 0.0630.016 Compound No. 1 rice 0 0 0 0 Barnyard 100 100 100 75 grass control2 rice 85 70 30 20 Barnyard 100 100 100 95 grass

Experimental Example 2

Rice[Oryza sativa. L. cv. Chuchong(ORYSA)] and barnyard grass[Echinocgloga crus-galli beauv. var. caudate Kitagawa(ECHCG) andEchinocgloa crus-galli Beauv. var. orygicola Ohwi (ECHOR)] were plantedand grown. The test compounds with 98% purity was dissolved in acetonecontaining tween-20 and diluted with water. Each maximum concentrationof acetone and tween-20 were 25% and 0.1%.

The solution was sprayed in a proportion of 200 g a.i per hactare on theleaves. When rice{ORYSA} had 6.0˜6.5 leaves with 32.8 cm of the firstleaf, barnyard grass(ECHOR) had 1˜2 tillering with 37.3 cm of the firstleaf and barnyard grass(ECHCG) had 1˜2 tillering with 44.4 cm of thefirst leaf.

20 and 30 days after treatment (DAT) herbicidal effect and toxicity weremeasured. The result is represented in the following table 8.

TABLE 8 Active Amount Treated activity (0˜100), 20 DAT toxicity (0˜100)Compound Formulation (%) amount ECHOR ECHCG 20 DAT 30 DAT Compound Tech.98% 200 100 99.5 0 0 control 1 Tech. 98% 200 100 100 22 39

As a result of these tests, the compounds of the present inventionexhibit an excellent selectivity toward rice and herbicidal activityagainst barnyard grass. And also it is proved that the compounds arevery stable for the plants and useful to control weeds.

What is claimed is:
 1. A method for preparing the compound (1) byreacting the compound of the formula (12) and the compound of theformula (13):

wherein, R is methyl or ethyl group; X is hydrogen, halogen, cyano,C₁˜C₆ alkyl, C₁˜C₆ alkoxy, C₁˜C₃ haloalkyl substituted with 1 to 3 ofhalogen atom(s), C₁˜C₃ haloalkoxy substituted with 1 to 3 of halogenatom(s), C₂˜C₄ alkoxyalkoxy, phenoxy, benzyloxy, C₂˜C₆ alkenyl, C₂˜C₆alkinyl, C₂˜C₆ alkenyloxy, C₂˜C₆alkinyloxy, or phenyl group; Y ishydrogen or fluoro; n is an integer of 1 or 2, when n is 2, X can be ina combination of other substituents; and Y′ is halogen,alkylsulfonyloxy, haloalkylsulfonyloxy, benzenesulfonyloxy ortoluenesulfonyloxy group.
 2. An intermediate compound of formula (13):

wherein, R is methyl or ethyl group; X is hydrogen, halogen, cyano,C₁˜C₆ alkyl, C₁˜C₆ alkoxy, C₁˜C₃ haloalkyl substituted with 1 to 3 ofhalogen atom(s), C₁˜C₃ haloalkoxy substituted with 1 to 3 of halogenatom(s), C₂˜C₄ alkoxyalkoxy, phenoxy, benzyloxy, C₂˜C₆alkenyl,C₂˜C₆alkinyl, C₂˜C₆alkenyloxy, C₂˜C₆alkinyloxy, or phenyl group; Y ishydrogen or fluoro; n is an integer of 1 or 2, when n is 2, X can be ina combination of other substituents.